Method for regulating plant growth

ABSTRACT

A process for regulating plant growth using pyrrolidinylcarboxanilides and pyrrolidinyl-thiocarboxanilides has been found. Both substituted and unsubstituted pyrrolidinyl carboxanilides and pyrrolidinyl-thiocarboxanilides can be used in the process.

United States Patent Pyne et a1. 1 1 Dec. 11, 1973 METHOD FOR REGULATING PLANT 2,829,146 4/1958 Beaver et a1 M 71/95 GROWTH 3,288,851 11/1966 Martin et al..... 3,318,947 5/1967 Speziale et a1 71/120 Inventors: William J. Pyne; James M. Gullo,

both of Painesville, Ohio; Bobby F. Adams, Pasadena, Tex.

Diamond Shamrock Corporation, Cleveland, Ohio Filed: Feb. 8, 1971 Appl. No.: 113,658

Related U.S. Application Data Assignee:

U.S. Cl. 71/95, 260/3263 Int. Cl A01n 9/22 Field of Search 71/95 References Cited UNITED STATES PATENTS 2/1972 Adams et a1 71/95 OTHER PUBLICATIONS Brown et al., Journal of American Chemical Society. 77, pp. 1079-1097 (1955) (cited by applicant).

Beaver et al., Journal of American Chemical Society, 79, pp. 1236-1245 (1957) (cited by applicant).

Chemical Abstracts, vol. 74, col. 99859Z 1971.

Primary Examiner-James 0. Thomas, Jr. Attorney-Roy Davis [57] ABSTRACT A process for regulating plant growth using pyrrolidinyl-carboxanilides and pyrrolidiny1-thiocarboxanilides has been found. Both substituted and unsubstituted pyrrolidinyl carboxanilides and pyrrolidinyl-thiocarboxanilides can be used in the METHOD FOR REGULATING PLANT GROWTH CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-impart of copending application Ser. No. 43,215, Pyne, Gullo, and Adams, filed June 3, 1970, now abandoned, which in turn is a continuation-in-part of application Ser. No. 8,152, Adams, Pyne, and Gullo (Case II), filed Jan. 19, 1970, and now abandoned, which in turn is a divisional application of Ser. No. 642,708, Adams, Pyne, and Gullo, filed June 1, 1967, and now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a method for regulating plant growth and more particularly to a process of applying to the locus of the unwanted plant growth such as weeds, a phytotoxic amount of a pyrrolidinylcarboxanilide or pyrrolidinyl-thiocarboxanilide.

2. Description of the Prior Art It is known that certain substituted ureas are useful in controlling weeds. For example, l-phenyl-3,3- dimethylureas which are substituted in the phenyl ring with halogen atoms are known to have good herbicidal action but are injurious to crops, hence have been restricted in use. Other ureas, for example, l-phenyl-3- (2-methylcyclohexyl)-urea that are known to be safe on beneficial plants have found very restricted use because of their limited herbicidal action.

SUMMARY OF THE INVENTION This invention is based on the unexpected discovery that pyrrolidinyl-carboxanilides and pyrrolidinyl-thiocarboxanilides of Formula (I):

in which R R and R are hydrogen or methyl or combinations of these provided at least one member is hydrogen, Z is oxygen or sulfur, Q is hydrogen, bromine, chlorine, fluorine, or iodine, and Y, X, and V are hydrogen, bromine, chlorine, fluorine, iodine, lower alkyl, alkoxy, halomethyl, cyano, or nitro with the proviso that Q is not fluorine when X, Y, and V are hydrogen and with the proviso that Q and V are not fluorine when X and Y are hydrogen, not only exhibit excellent herbicidal action but when applied at suitable rates also are very useful as selective herbicides to control the growth of undesirable plants and weeds in areas where important crops such as corn, rice, sorghum, cotton, peanuts, sugar beets, potatoes, beans such as field, dry and snap beans, small grains, sugar cane, bananas, cof fee, pineapples, vegetables, fruit (including deciduous fruit), nut, citrus and other trees are being grown. Unless otherwise indicated, all other substituents in the formula are hydrogen.

It is an object of this invention to provide a process for regulating plant growth using pyrrolidinylcarboxanilides and pyrrolidinyl-thiocarboxanilides. Another object is to provide a process for regulating unwanted plant growth using a selective herbicide. A further object is to provide a composition containing a selective herbicide and a process for its use. Other ob- DESCRIPTION OF THE PREFERRED EMBODIMENTS Accordingly, the present invention provides compounds of the above formula and also herbicidal compositions which can be admixtures of such a compound with a solid or liquid diluent or solutions of such a compound in liquid or solid solvents. These compounds can be used in undiluted form or can be formulated using the procedures and adjuvants described in U. S. Pat. No. 3,419,626, Pyne and Bluestone, issued December 31, 1968, in C01. 2, line 57, through Col. 4, line 2. The formulations may also contain suitable surfactants (surface active agents), other pesticides or growth regulants, fertilizer, spray oil, adhesives, other adjurants. These herbicidal compositions can contain from about 0.01 percent to about 99 percent by weight of the pyrrolidinyl'carboxanilide or pyrrolidinyl-thiocarboxanilide as the active ingredient.

Plant growth is regulated by applying a phytotoxic amount of the above pyrrolidinyl-carboxanilides or pyrrolidinylthiocarboxanilides to the locus of the plant growth. These compounds or their formulations are ap plied directly to the foliage when used as postemergence herbicides and are applied to soil when used as preemergence herbicides. The compounds can be applied in the form of sprays, drenches, dusts, emulsions, dispersions, suspensions, solutions, or in any other suitable form. The compounds are effective as herbicides when applied to plant growth or soil at rates of from about one-sixteenth to about 16 lb/A (pounds per acre) and particularly at rates from about one-fourth to about 4 lb/A.

Compounds of the above general formula can be prepared by known synthetic methods including those used commercially for the preparation of other ureas. A few methods are described below by way of illustration but are not intended to be an exhaustive list of suitable methods:

| 1 T H s 1 u Ar-NCS HN\ Ar-N-CN\ .mlfT a v l where Ar is substituted or unsubstituted phenyl such as phenyl, 4-bromophenyl, 2-chlorophenyl, 3- chlorophenyl, 4chlorophenyl, B-fluorophenyl, 4-

3 fluorophenyl, 4-iodophenyl, 3-methylphenyl, 4- cyanophenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3- nitrophenyl, 4-nitrophenyl, 3,4-dich1oropheny1, 2,4- difluorophenyl, 3-trifluoromethylphenyl, 2-chloro-5- 100 ml of anhydrous benzene with phenylisothiocyanate (13.5 g, 0.1 m). After the slight exothermic reaction subsides, the reaction mixture is heated to reflux for 3 hours, cooled, and solvent removed at reduced trifluoromethylphenyl, 2,3,4,5-tetrafluorophenyl, and 5 pressure. The residual solid is crystallized from a penthe like. lane-benzene mixture to give 14 g (60 percent yield) of Pyrrolidines include pyrrolidine, cis-2,5-dimethylpyr- Compound No. 5351, a solid melting at l04l05 C. rolidine, cis-2,4-dimethylpyrrolidine, and the like. Compound No. 5351 (C, H, N S) Calculated: N,

Reference may also be made to the examples for a 119; Found: N, 12.1 percent. fuller understanding of the invention. The examples are 10 EXAMPLE 3 given merely to illustrate the invention and are not to be construed in a limiting sense. All percentages, quan- The Procedures given Examples 1 and 2 for the tities, parts, and proportions are by weight and all tem- Preparatlon of Compound 5328 and Compound peratures are C unless otherwise indicated. 5351. p yv are used to P p pounds as well as the other compounds shown in Table EXAMPLE 1 1 below. This table gives the compound type, compound number, chemical name, empirical formula, per- Preparation of o cent yield, melting point C), N percent calculated 1-(cis-2 ,S-dtmethylpyrrohdmyl )-carboxan1l1de and N percent found for these compounds. The com- (Compound No. 5328) by Procedure (a) pound Type 1 products are prepared by reacting the ap- Phenyl lsocyanate g. 0.092 is reacted m 100 propriate phenylisocyanate or phenylisothiocyanate ml of anhydrous benzene with cis-2,5-dimethylpyrroliwith pyrrolidine whereas the compound Type 11 proddine g, 0092 P p from ,5- ucts are obtained by reaction of the appropriate isocyadimethylpyrrole y procedur of C. Over rger et nates with cis-2,5-dimethylpyrrolidine and the com- JACS, 4102 This mixture is heated t0 pound Type 111 products are obtained by reaction ofthe reflux for 3 hours. Cooled. filtered, and Solvent appropriate isocyanates with cis-2,4-dimethylpyrrolimoved at reduced pressure. The residual solid is crysdine. Cis-2,4-dimethylpyrrolidine is obtained by reductallized from a benzene-petroleum ether mixture to tion of 2,4-dimethylpyrrole using the procedure degive 13 g (64 percent yield) of Compound No. 5328, scribed by C. G. Overberger et al in JACS, 77, 4102 a solid melting at 109-110 C. Compound No. 5328 (1958) for the cis-2,S-dimethylpyrrolidine; 2,4- (C H N O) Calculated: N, 12.8 percent; Found: N, dimethylpyrrole is prepared by the procedure given in 13.2 percent. Organic Synthesis, Collective Vol. 11, page 217.

TABLE 1 Com- Melting N (percent) pound Empirical Percent point, number Chemical name formula yield C. Calcd. Found 3961 1-pyriolidinylcarboxanilide CHIIHNQO 01 130-131 4300 l-pyrrolidinylthiocnrboxanilidu. CHIIHNQS 03 149-150 4391 l-pyrrolidinyl-3-chlorocarboxanilide.. CHIIUCINQO 01 143-144 4392 l-pyrrolidinyl-3,4-dichlororcurboxanilido CIII'IIQCI'ZNZO 78 179-180 4874 l-pyrrolidiny1-4-eh10rocarboxanilide 0111113011120 100 167-168 12.5 12.3 4888 l-pyrrolidinyl-3-trifluor0methylcarboxanilide CHI'IIJFJN'JO 67 160-161 10.8 10.8 17025 l-pyrrolidinyl-2-chloro-5-trifluoromethylcarvoxun d0. CIQIIHCIFSNQO 68 104-105 11.7 10.0 5166 1-(cis-2,5-dimethylpyrrolidinyl)-3-methylcarboxanilide. CHHQUNQO 76 73-75 12.1 12.7 5168 1(cis-2,5-dimethylpyrrolidinyl)-4-chlorocarboxanilide. C13I111C1Nz0 84 148-140 11.1 10.0 5171 1-(cis-2,5-dimethylpyrrolidinyl)-3-chlorocarboxanilide Ci HnClNgO 81 118-110 11.1 11.4 5177 1-(cis-2,5-dimethylpyrrolidinyl)-4-methoxycarhoxanilidc CHIIQONZOZ 80 110-112 11.3 12.1 5307 1-(cis-2,5-dlmethylpyrrolidinyl)-3,4-dichlorocarboxanilld0.. C1JII|6C12N2O 78 137-138 9.7 9.7 5327 1-(cis-2,5-dimethylpyrrolidinyl)-3-meth0xycarboxanilide CHIIQONQO? 61 104-106 11.3 1.3 5328 1-(c1s-2,5-dimcthylpyrrolidinyl)-carboxanilide CHIIIBNQO 109-110 12.8 13.2 5351 1-(cis-2,5-(limethylpyrrolidinyl)-thiocarboxani1ide CHHHNQS 00 104-105 12. 0 12. 1 5372 1-(ciS-2,5-d1methylpyrrolidinyl)-4'-cyanocarboxanilide CHIIHNJO 41 160-161 17.3 17.1 5374 1-(cis-2,5-dimethylpyrrolidinyl)-4-fluorocarboxani]ide C13II17FNQO 135 11.0 11.5 5370 1-(cis-2,5-dimethylpyrrolidinyl)-3-trif1uoromcthylearboxanilide CHIIHFJNZO -130 11.8 10.0 5301 1-(cis-2,5-dimethylpyrrolidinyl)-3trifluoromcthylthiocnrboxanilid Cn lInFa Nr v 1 5403 1-(eis-2,5-dimethylpyrroll(1inyl)-4-nitrocarboxanilide CglInNgO; 08 114-116 16.0 16.3 5456 1-(c1s-2,5-d methylpyrrolidinyl)-4-brorn0carboxanilide cnl-lnBrNzO 88 131-132 0.4 0.. 5451 1-(c s-2,5-d1meLhylpyrrolidinyl)2-chlorocarboxanilide CnHnClNuO J3 011 11.1 10.4 5460 l-(crs-Zj-drmethylpyrrolidiuyl)-3-nitrocarboxanilide C13Hi'iN303 84 -131 16.0 16.1 16654 1-(c s-Z,fi-d methylpyrrolidinyl)-3-fluor0carboxanilide. CIIIIIHFNQO 54 117-118 11.7 11.8 16947 1-(c s-2,fi-d methylpyrrolidinyl)-4-iodocarboxanilide CIJI'IHINQO 87 134-135 8.1 7.7 17256 1-(c1s-2,5-d1methylpyrr0lidinyl) -2-4-difiuorocarbo.\'ani C1311 mFgNgO 54 78-80 17836 l-(c s-2,5-d methy1pyrr01idinyl)-2,3,4,5tetrafiuorocarbox. CIQHHFJNQO 58 102-106 9. 7 .1. 6 5498 1-(c1s-2,4-d1methylpyrrolidinyl)-3-chlorocarboxanilide CnHnclNgO 03 Oil 11.1 11.0 5500 1-(c s-2,4-d methylpyrrolidinyl)-4-ch1orocarboxanilidc. CIQI'IflClNEO 05 130 11. 1 11.4 5510 1-(c s-2,4-d methylpyrrolidinyl)-4-l romocarboxanilide CnHnBrNzo 81) 11.4 0.3 5511 1-(c1s-2,4-d methylpyrrolidinyl)-carb0xnnilide CnHlaNzO 85 113-114 12. 8 13. 0 5512 1-(c s-2,4-d methylpyrrolidinyl)-4-flu0r0carl)0xanilide. C13H17FN'JO 57 95 4.16 11. U 11. 7 5524 1-(c1s-2,4-d1methylpyrrolidinyl)-3,4-dichlorocarboxanilid CnH ChNaO 66 124-129 9.8 9.5

EXAMPLE 2 EXAMPLE 4 Preparation of Greenhouse Herbicide Tests 1-( cis-2,5 -dimethylpyrrolidinyl )-thiocarboxanilide (Compound No. 5351) by Procedure (c) Cis-2,S-dimethylpyrrolidine (9.9 g, 0.1 m) prepared by the procedure described in Example 1 is reacted in Test formulations are prepared by mixing 20 ml of an 65 acetone solution containing 0.083 g of the test compound with 20 ml of water containing 0.01 g of Triton X-155 surfactant. The resultant formulations contain 5 6 2080 ppm of test compound, 50 percent volume of ace- LE 2 Al -u t ed tone and 0025 percent y weight of Surfactant APPTO' Postemerueuce weed control (percent) priate lower concentrations are obta ned by diluting Brow-[leaves W3.) Grasses (lb-3a.) the stock formulation; the concentration of ad uvants Compound number 4 1 0.25 4 1 0.2.: are maintained at these levels, r

":3 0 o o u A. Preemergence Test on 01:11:: IIIIZIQIIIIIIL Seeds of three broadleaf and three grass species are 15 a-(1% l) J l planted 1n soil contained in 9 inches X 9 inches X 2 8 inches aluminum pans filled with 1% of composted soil. The broadleaf species are buckwheat (Fagopyrum TABLE 3 esculentum), turnip (Brassica rapa) and Zinnia (Zinnia Posmuomnce Wm comm} (percent) spp. the grasses are Italian millet (Panzcum ramosum), Broadlmves in/m) Grasses (L perennial ryegrass (Lolzum perenne) and sorghum C 1 v 3 1 3 (Sorghum vulgare). 01111011! 11m g The pans are then sprayed so that the soil surface is g8 g uniformly covered with 40 ml of the stock formulation 5 3 g8 g8 5 5) o to obtain a treatment rate of 16 lb/acre of the test com- {i O pound or appropriate dilutions of same to obtain the g3 i8 8 lower treatment rates with the test compounds shown 4 l 0 a, 4 1 O T in Table 2. Two weeks after treatment, percent control 100 100 100 00 u." 10 estfmatefi 100 100 100 so u; 0 Using this procedure, the results shown in Table 2 are 100 100 1.0g 6: s5 100 100 a. 3.1 u 0 obtained. These data show preemergence weed control 100 1 0 95 (2| (,0 15 (percent) obtained with broadleaves and grasses USilg 183 4 .JT s s A, 4, l, and 0.25 lb/A treatments of the test compoun s. m0 10(1) 97 95 U u 100 100 so 100 o B. Postemergence Test 100 100 65 w 1.3 n no as 0 10 u Aluminum pans 9 inches X 9 inches X 2 inches, as described in Example 4A, are transferred to the green- 7;; 0 so 0 11 house where the test species are allowed to grow until 100 f}; ",3- 68 8 "5 one true leaf is present on the slowest growing broad- 8; g t; leaf (Zinnia). This requires 7-14 days depending on the u 0 n 0 Season of the y 100 "WEXTIIIIIII 3i ".5111:

The pans are then sprayed so that the soil surface and i foilage are uniformly covered with 40 ml of the stock '33 13 formulation l6 lb/acre) or appropriate dilutions of the same as described in Example 4A to obtain the lower Rates l ytreatment rates with the test compounds shown in 40 Table EXAMPLE 5 Using this procedure, the results shown in Table 3 are Fied Tests obtained. These data show postemergence weed control (percent) obtained with broadleaves and grasses A field which has been cleared of all annual weeds using 6, 4, 3, 1.5, l,and 0.25 lb/A treatments of the test before the test is sown with the following crop and compounds. weed plants: (crops) corn (Zea mays); (broadleaved weeds) redroot pigweed (Amaranthus retroflexus), prickley sida (Sida spinosa), wild mustard (Brassica kaber), velvetleaf (Abutilon theophrasti), purslane TABLE 0 5O (Portulaca oleracea); (grass and sedge) crowfoot grass (Dactyloctenium aegyptium) and annula sedge Pmmegem Weed (9mm) (Cyperus compressus). On the day before sowing, the Broadleaves lit/a.) Grasses (ill/a.) field is treated with aqueous suspensions prepared from Compound number 4 1 ,25 4 1 035 percent wettable powders of the various test compounds and commercial herbicide standards shown in Table 4. The herbicide test compounds and standards are incorporated by raking in two directions each at a 90 angle to one another. The active substance is applied at the rate of 4.0, 2.0, 1.0, and 0.5 pound per acre (lb/A). Eight weeks after treatment, the degree of damage to all the test plants is assessed according to a scale of values from O to 10; O denoting a completely normal plant, and 10 denoting complete destruction. The degrees of damage to the crops, broadleaved weeds, grass 0 and sedge described above are shown in Table 4.

TABLE 4.PREEMERGENCE HERBICIDE FIELD TESTS Weed control 1 Crop injury 1 Broadleaves (lb./a.) Grasses and sedge (lb./a.) Corn (lb./a.)

Compound tested 4. 2.0 1.0 0. 4. 0 2. 0 1.0 0.5 4. 0 2. 0 1.0 0. a

10 9 8 1O 1O 9 7 0 0 0 O 10 10 10 9 10 10 10 7 O O O 0 10 7 8 7. 5 l0 8 7 5 O O 0 0 17836 10 10 8 7 l0 7 5 O 2 0 0 0 STANDARDS:

Fluometuron 2 (80% WP) 10 9 8 8 10 10 1O 10 10 10 10 10 Llnll10n (50% WP) 10 10 10 10 10 10 10 8. 5 8 8 8 8 Diuron 4 (80% WP) 1O 10 1O 9. 5 10 10 8 7 10 10 10 9 1 Average weed control and crop injury of three replications (Pro-Plant Incorporated) using scale oiO to 10 where 0 is a completely normal plant and 10 is complete destruction.

1 3-(3-triiloromothylphenyD-l,l-rliinethyluroa as 80% 3 3-(3,4-dichlorophonyl)-1-mothoxy-l-methyluroa as 50% WP (wettable 3-(3,4-dichlorophenyl)-1,1dimethylurca as 80% WP (wettable powder What is claimed is:

1. A process of regulating plant growth which comprises applying to the locus of the plant growth a phytotoxic amount of a compound having the formula:

wherein R R and R are selected from the group con sisting of hydrogen, methyl, and combinations thereof provided at least one member is hydrogen; Z is selected from the group consisting of oxygen and sulfur; Q is selected from the group consisting of hydrogen, bromine, chlorine, fluorine, and iodine; Y, X, and V are selected from the group consisting of hydrogen, bromine, chlorine, fluorine, iodine, lower alkyl, alkoxy, halomethyl, cyano, nitro substituents and combinations thereof with the proviso that Q is not fluorine when X, Y, and V are hydrogen and with the proviso that Q and V are not fluorine when X and Y are hydrogen.

2. The process of claim 1 wherein the compound is l-(cis-2,S-dimethylpyrrolidinyl)-carboxanilide.

3. The process of claim 1 wherein the compound is l-(cis-2,5-dimethylpyrrolidinyl)-4'- fluorocarboxanilide.

W1 (wettable powder).

powder).

4. The process of claim 1 wherein the compound is 1-(cis-2,4-dimethylpyrrolidinyl)-4'- fluorocarboxanilide.

5. The process of claim 1 wherein the compound is l-(cis-2,S-dimethylpyrrolidinyl)-4'- chlorocarboxanilide.

6. The process of claim 1 wherein the compound is l-(cis-2,5-dimethylpyrrolidinyl)-3-trifluoromethylcarboxanilide.

7. The process of claim 1 wherein the compound is l-( cis-2,S-dimethylpyrrolidinyl )-3 fluorocarboxanilide.

8. The process of claim 1 wherein the compound is l-(cis-Z ,5-dimethylpyrrolidiny1)-4 iodocarboxanilide.

9. The processof claim 1 wherein the compound is used as a selective herbicide on com.

10. The process of claim 1 wherein l-(cis-2,5- dimethylpyrrolidinyl)-3'-fluorocaroxanilide is used as a selective herbicide on corn.

11. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-3 ',4- dichlorocarboxanilide.

12. The process of claim 1 wherein the compound is l-(cis-2,5-dimethylpyrrolidinyl)-4- cyanocarboxanilide.

13. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-4'- bromocarboxanilide. 

2. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-carboxanilide.
 3. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-4''-fluorocarboxanilide.
 4. The process of claim 1 wherein the compound is 1-(cis-2,4-dimethylpyrrolidinyl)-4''-fluorocarboxanilide.
 5. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-4''-chlorocarboxanilide.
 6. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-3''-trifluoromethylcarboxanilide.
 7. The process of claIm 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-3''-fluorocarboxanilide.
 8. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-4'' -iodocarboxanilide.
 9. The process of claim 1 wherein the compound is used as a selective herbicide on corn.
 10. The process of claim 1 wherein 1-(cis-2,5-dimethylpyrrolidinyl)-3''-fluorocaroxanilide is used as a selective herbicide on corn.
 11. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-3'',4''-dichlorocarboxanilide.
 12. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-4''-cyanocarboxanilide.
 13. The process of claim 1 wherein the compound is 1-(cis-2,5-dimethylpyrrolidinyl)-4''-bromocarboxanilide. 